Isotopic and chromatographic fingerprinting of the sources of dissolved organic carbon in a shallow coastal aquifer

The terrestrial subsurface is the largest source of freshwater globally. The organic carbon contained within it and processes controlling its concentration remain largely unknown. The global median concentration of dissolved organic carbon (DOC) in groundwater is low compared to surface waters, suggesting significant processing in the subsurface. Yet the processes that remove this DOC in groundwater are not fully understood. The purpose of this study was to investigate the different sources and processes influencing DOC in a shallow anoxic coastal aquifer. Uniquely, this study combines liquid chromatography organic carbon detection with organic (δ13CDOC) carbon isotope geochemical analyses to fingerprint the various DOC sources that influence the concentration, carbon isotopic composition, and character with respect to distance from surface water sources, depth below surface, and inferred groundwater residence time (using 3H activities) in groundwater. It was found that the average groundwater DOC concentration was 5 times higher (5 mg L−1) than the global median concentration and that the concentration doubled with depth at our site, but the chromatographic character did not change significantly. The anoxic saturated conditions of the aquifer limited the rate of organic matter processing, leading to enhanced preservation and storage of the DOC sources from peats and palaeosols contained within the aquifer. All groundwater samples were more aromatic for their molecular weight in comparison to other lakes, rivers and surface marine samples studied. The destabilization or changes in hydrology, whether by anthropogenic or natural processes, could lead to the flux of up to 10 times more unreacted organic carbon from this coastal aquifer compared to deeper inland aquifers

A new conceptual framework for the transformation of groundwater dissolved organic matter

Groundwater comprises 95% of the liquid fresh water on Earth and contains a diverse mix of dissolved organic matter (DOM) molecules which play a significant role in the global carbon cycle. Currently, the storage times and degradation pathways of groundwater DOM are unclear, preventing an accurate estimate of groundwater carbon sources and sinks for global carbon budgets. Here we reveal the transformations of DOM in aging groundwater using ultra-high resolution mass spectrometry combined with radiocarbon dating. Long-term anoxia and a lack of photodegradation leads to the removal of oxidised DOM and a build-up of both reduced photodegradable formulae and aerobically biolabile formulae with a strong microbial signal. This contrasts with the degradation pathway of DOM in oxic marine, river, and lake systems. Our findings suggest that processes such as groundwater extraction and subterranean groundwater discharge to oceans could result in up to 13 Tg of highly photolabile and aerobically biolabile groundwater dissolved organic carbon released to surface environments per year, where it can be rapidly degraded. These findings highlight the importance of considering groundwater DOM in global carbon budgets

The effect of microbial activity and adsorption processes on groundwater dissolved organic carbon character and concentration

Balancing the terrestrial global carbon budget has proven to be a significant challenge. Whilst the movement of carbon in the atmosphere, rivers and oceans has been extensively studied, the potential for groundwater to act as a carbon source or sink through both microbial activity and sorption to and from mineral surfaces, is poorly understood.To investigate the biodegradable component of groundwater dissolved organic carbon (DOC), groundwater samples were collected from multiple coastal and inland sites. Water quality parameters such as pH, electrical conductivity, temperature, dissolved oxygen were measured in the field. Samples were analysed and characterised for their biodegradable DOC content using spectrofluorometric and Liquid Chromatography-Organic Carbon Detection (LC-OCD) techniques at set intervals within a 28 day period.Further to this, we performed laboratory sorption experiments on our groundwater samples using different minerals to examine the effect of adsorption processes on DOC character and concentration. Calcium carbonate, quartz and iron coated quartz were heated to 400ºC to remove potential carbon contamination, and then added at various known masses (0 mg to 10 g) to 50 mL of groundwater. Samples were then rotated for two hours, filtered at 0.2 μm and analysed by LC-OCD.This research forms part of an ongoing project which will assist in identifying the factors affecting the mobilisation, transport and removal of DOC in uncontaminated groundwater. By quantifying the relative importance of these processes, we can then determine whether the groundwater is a carbon source or sink. Importantly, this information will help guide policy and identify the need to include groundwater resources as part of the carbon economy

Sorption of Groundwater Dissolved Organic Carbon onto Minerals

Our understanding of groundwater organic matter (OM) as a carbon source or sink in the environmental carbon cycle is limited. The dynamics of groundwater OM is mainly governed by biological processing and its sorption to minerals. In saturated groundwaters, dissolved OM (DOM) represents one part of the groundwater organic carbon pool. Without consideration of the DOM sorption, it is not possible to quantify governing groundwater OM processes.This research explores the rate and extent of DOM sorption on different minerals. Groundwater DOM samples, and International Humic Substances Society (IHSS) standard solutions, were analysed. Each was mixed with a range of masses of iron coated quartz, clean quartz, and calcium carbonate, and shaken for 2 hours to reach equilibrium before being filtered through 0.2 μm for total dissolved organic carbon (DOC) and composition analysis by size-exclusion chromatography-organic carbon detection (LC-OCD). Sorption isotherms were constructed and groundwater DOM sorption were compared to the sorption of IHSS standards.Initial results suggest that for the IHSS standards, the operationally-defined humic substances fraction had the strongest sorption compared to the other LC-OCD fractions and total DOC. Some samples exhibited a small increase in the low molecular weight neutral (LMW-N) aqueous concentration with increasing humic substances sorption. This gradual increase observed could be the result of humic substances desorbing or their breakdown during the experiment. Further results comparing these IHSS standards with groundwater samples will be presented.In conjunction with complementary studies, these results can help provide more accurate prediction of whether groundwater OM is a carbon source or sink, which will enable the management of the groundwater resources as part of the carbon economy

Insights in groundwater organic matter from Liquid Chromatography-Organic Carbon Detection

Understanding the processes that control the concentration and characteristics of organic matter in groundwater has important implications for the terrestrial global carbon budget. Liquid Chromatography – Organic Carbon Detection (LC-OCD) is a size-exclusion based chromatography technique that separates the organic carbon into molecular weight size fractions of biopolymers, humic substances, building blocks (degradation products of humic substances), low molecular weight acids and low molecular weight neutrals. Groundwater and surface water samples were collected from a range of locations in Australia representing different surface soil, land cover, recharge type and hydrological properties. At one site hyporheic zone samples were also collected from beneath a stream.The results showed a general decrease in the aromaticity and molecular weight indices going from surface water, hyporheic downwelling and groundwater samples. The aquifer substrate also affected the organic composition. For example, groundwater samples collected from a zone of fractured rock showed a relative decrease in the proportion of humic substances, suggestive of sorption or degradation of humic substances.This work demonstrates the potential for using LC-OCD in elucidating the processes that control the concentration and characteristics of organic matter in groundwater

The role of dissolved organic matter and groundwater biogeophysical processes in the carbon budget.

Title: The role of dissolved organic matter and groundwater biogeophysical processes in the carbon budget.Phetdala Oudone , , Christopher E. Marjo , Karina Meredith , Liza McDonough1,2, Helen Rutlidge2, , Martin S Andersen2,5, Denis O`Carroll2,5, Andy Baker1,2. Atmospheric CO2 concentration is acknowledged to play an important role in climate change. However, quantifying more accurate predictions requires a sound understanding of the cycle and process of carbon especially in the environment. There has been extensive research on terrestrial carbon and the different conditions where it is a source or sink. However, the knowledge on whether groundwater organic matter is a carbon source or sink is limited. This work will explore the dynamic of groundwater organic matter including both its concentration and its rate and extent of biological processing and sorption. The UNSW Wellington Research Station was selected for groundwater sampling as it represents a fractured rock aquifer and alluvial aquifer for groundwater property and interaction investigation. Samples were collected from a transect of boreholes perpendicular from the river. Literature procedures were adopted for determining biological dissolved organic carbon and investigation of organic matter sorption on pure minerals (quartz sand, iron-coated quartz sand and calcium carbonate). For each sample collected total dissolved organic concentration was measured and the organic matter present was characterized by fluorescence spectroscopy and size-exclusion chromatographic technique, LC-OCD. There was greater sorption of organic matter with calcium carbonate, followed by iron-coated sand, while minimum sorption was observed with sand. This research in conjunction with similar studies in different environments will allow conclusions to be drawn groundwater organic matter and whether it is a carbon source or sink and thereby the findings can eventually have some policy application which will enable the management of the groundwater resources as part of the carbon economy